Matte-surfaced polyester sheeting



Feb. 27, 1968 E c. R. HASENAUER ETAL 3,370,95i

MATTE-SURFACED POLYESTER SHEETING Filed Nov. 21, 1966 H /MATTE SURFACE m V-SUBSTRATUM LAYER POLYESTER SUPPORT 28 LIGHT-SENSITIVE LAYER TIN LAYER MATTE LAYER SUBSTRATUM LAYER POLYESTER SUPPORT LIGHT-SENSITIVE LAYER MATTE LAYER SUBSTRATUM LAYER POLYESTER SUPPORT Fig; 3

Charles R. Hasenauel' Wal fer R.Wh i te IN V EN TORS United States Patent 0 3,37%,951 hiATTE-fiilllRFAtIEl) POLYESTER SHEETING Charles R. Hasenauer and Walter R. White, Rochester,

N.Y., assiguors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Continuation-impart of application Scr. No. 218,650, Aug. 22, 1962. This application Nov. 21, 1966, Ser. No. 611,494

17 Claims. (Ci. 96-87) This application is a continuationin-part of US. patent application Ser. No. 218,650 filed Aug. 22, 1962, now abandoned.

This invention relates to polyester sheeting provided with a matte surface or layer and to the method of preparing the same. This invention relates also to a composition of matter for use in providing a matte surface or layer on polyester sheeting.

An object of this invention is a matte-surfaced polyester sheeting.

Another object of this invention is a composition of matter for use in providing a matte surface on polyester sheeting.

A further object of this invention is a method of producing on polyester sheeting a matte surface that will take drawing ink and hard pencil designs without smudging.

A still further object of this invention is a photographic film product comprised of the matte-surfaced polyester sheeting of this invention and a light sensitive silver halide emulsion layer.

Other objects of this invention will, in part, be obvious and will, in part, appear hereinafter.

For a complete understanding of the nature and the objects of this invention, reference is made to the following detailed description and drawing, in which:

FIG. 1 is a view in cross-section of the matte-surfaced polyester sheeting of this invention.

FIG. 2 is a view in cross-section of a photographic film product comprised of the matte-surfaced polyester sheeting of this invention.

FIG. 3 is a view incross-section of another photographic film product comprised of the matte surfaced polyester sheeting of this invention.

In accordance with this invention there is provided a composition of matter which, in a suitable vehicle therefor, can be applied to a subbed surface of polyester sheeting to provide thereon, after drying, a matte surface or layer.

The matte-surfaced polyester sheeting can be per se employed as a member on which ink and pencil drawings can be made, or it can be overcoated with a suitable unhardened light-sensitive silver halide emulsion to provide a photographic film product for use in the photographic reproduction art. The light sensitive layer can be comprised of gelatin and a silver halide such as silver chloride, silver bromide, silver chloro-bro-mide and silver iodobromide and is capable of treatment by light-printing and subsequent development to form an image, the gelatin of the image areas being hardened to resist removal during washing. The developed image is commonly the lines of a drawing or the like. That is, the image is a positive one with considerable background or area which is free from image. The area that is free from image is removed after development, by washing for example with warm water to lay bare the matte surface for pencil or ink corrections, additions, and the like. The formed image can be easily removed by a rubber eraser if desired. It is also sometimes advantageous to have the matte surface on both sides of the sheeting, even though only one side is to be sensitized.

Suitable sheeting for use in this invention can be prepared from high molecular weight polyesters derived by condensing a dihydric alcohol with a dibasic saturated fatty carboxylic acid or derivatives thereof. Suitable dihydric alcohols for use in preparing polyesters are well known in the art and include any glycol wherein the hydroxyl groups are on the terminal carbon atom and contain from 2 to 12 carbon atoms such, for example, as ethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, decamethylene glycol, dodecamethylene glycol, and 1,4-cycl0hexane dimethanol. Dibasic acids that can be employed in preparing polyesters are well known in the art and include those dibasic acids containing from 2 to 16 carbon atoms. Specific examples of suitable dibasic acids include adipic acid, sebacic acid, isophthalic acid, and terephthalic acid. The alkyl esters of the aboveenurnerated acids can also be employed satisfactorily. Other suitable dihydric alcohols and dibasic acids that can be employed in preparing polyesters from which sheeting can be prepared are described in J. W. Wellman, US. Patent No. 2,720,503, dated Oct. 11, 1955.

Specific examples of polyester resins which, in the form of sheeting, can be used in this invention are polyethylene terephthalate, poly(1,4-cyclohexyldimethylene terephthalate), and the polyester derived by reacting 0.83 mol of dimethyl terephthalate, 0.17 mol of dimethyl isophthalate and at least one mol of l,4-cycloheXanedimethanol. Patent 2,901,466, reference to which is hereby made, discloses polyesters prepared from 1,4-cyclohexanedimethanol and their method of preparation.

The thickness of the polyester sheet material employed in carrying out this invention is not critical. Polyester sheeting of a thickness of from about 2 mils to 50 mils can be employed satisfactorily. Usually, for photographic products, the thickness of the polyester sheeting used will be of the order of from about 3 to 5 mils.

Polyesters, and particularly polyethylene terephthalate are very hydrophobic, and the polyester sheeting used in this invention must be provided with an intermediate anchoring layer thereon prior to the application thereto of the matte surface or matte layer. An intermediate anchoring layer is often referred to in the art as a subbing layer, a sub layer, or a substratum layer.

Resins and resin compositions for use in providing anchoring layers or sub layers on a surface of polyester sheeting are well known in the art but nevertheless constitute a part of this invention. A suitable resin for this purpose is a copolymer comprised of, by weight, from about 35 percent to 96 percent of vinylidene chloride, from about 3.5 percent to 64.5 percent of an ethylenically unsaturated ester (also referred to as an acrylic ester), and from about 0.5 to 25 percent of itaconic acid or the half methyl ester of itaconic acid, acrylic acid, or methacrylic acid. The ethylenically unsaturated esters can be acrylonitrile, methacrylonitrile, vinylchloride, and alkyl esters of acrylic and methacrylic acids having 1 to 18 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. A copolymer of the above type that has been used satisfactorily in carrying out this invention is a copolymer of methyl acrylate, vinylidene chloride, and itaconic acid, a specific example of such copolymer being one comprised of, by weight, about 15 percent of methyl acrylate, about 83 percent of vinylidene chloride, and 2 percent of itaconic acid.

To establish and maintain adequate and satisfactory adhesion of the sub layer to a surface of the polyester sheeting to which it is applied, an adhesion promoter can be incorporated therein prior to application thereof to a surface of the polyester sheeting. The subbing resins as above described are usually applied from a water dispersion (often referred to as a latex) thereof. The amount of adhesion promoter employed will be from about 0.1 percent to 5 percent by weight based on the weight of the subbing resin. Water is employed as a vehicle or carrier for the copolymer and the adhesion promoter when applied to the polyester sheet material. The water is subsequently removed from the applied coating by drying.

Examples of suitable adhesion promoters for this purpose include resorcinol, orcinol, catechol, pyrogallol, 1- naphthol, 2,4-dinitrophenol, 2,4,6-trinitrophenol, 4- chlororesorcinol, 2,4-dihydroxytoluene, 1,3-naphthalenediol, 1,6-naphthalenediol, acrylic acid, the sodium salt of l-naphthol-4-sulfouic acid, benzyl alcohol, trichloroacetic acid, o-hydroxybenzotrifluoride, m-hydroxybenzotrifluoride, o fluorophenol, m fiuorophenol, p fluorophenol, chloro hydrate, and o-cresol. Mixtures of two or more adhesion promoters can be employed if desired.

To the subbed surface of the polyester sheet material there is applied the matte coating composition of this invention. Water is employed as a carrier or vehicle for the matte coating composition and after application thereof by conventional means such, for example, as by bead application, by roll coating. by air knife doctor means, and the like, the thus-applied matte coating composition is dried to remove therefrom substantially all the water.

Drying of the applied coating is conveniently accomplished by impinging hot air maintained at a temperature from about 170 F. to 250 F. on the uncoated side of the polyester sheet material. The applied coating is thus dried by conduction heat transfer. It has been determined that by employing the conduction heat transfer method of drying the applied matte coating composition there is provided a matte surface or matte layer that is substantially free of cracks and crazing. It is well known to those skilled in the art that matte surfaces that are cracked or crazed are highly unsatisfactory in use, as the cracks or crazing tend to make difiicult the removal by erasure of pencil or ink drawings applied thereto.

The matte composition of this invention is comprised of, by Weight, from about 5 to 30 parts of a vinylidene chloride copolymer from about 1 part to 25 parts of a finely divided abrasive material such as silica having an average particle size of from about 2.5 to microns and from about 0.1 to 0.5 part of a thickening agent. Such additional materials as from about 0.15 part to 6 parts of an insoluble whitening pigment such as a titanium dioxide pigment, and/or from about 0.10 to 1.0 part of a dispersing or wetting agent, can also be utilized to advantage in certain preferred embodiments of this invention.

Water is conveniently employed as a carrier or a vehicle for the matte composition to provide a coating composition thereof. Aqueous coating compositions comprised of, by weight, from about 50% to 75% of Water are satisfactory. Aqueous coating compositions comprised of, by weight, about 35% of solids and 65% of water have proved highly satisfactory in use.

While the above matte composition will provide a satisfactory matte surface or coating on polyester sheeting, the final product usually possesses a yellow hue. To mask or neutralize this yellow hue and to give the final product a more pleasing color, it is recommended that a blue pigment, or a violet pigment or mixtures thereof be incorporated in the matte composition prior to application thereof. The type and amount of pigment to be employed is within the skill of those versed in the art. A matte composition comprised of from about 0.004 to 0.05 part by weight of pigment has proved satisfactory in use. A suitable blue pigment is one having a new color index of 74160 such, for example, as Monarch Blue Toner NCX2371. A suitable violet pigment is one having a color index pigment violet 19 such, for example, as Monastral Violet R RT 7330.

A bactericide can be incorporated in the aqueous coating composition if desired to destroy mold, fungus. and the like. A bactericide is employed in an amou t suffic ent to provide a composition comprised of. by weight, from about .001 to .01 part of bactericide. Suitable bactericides are known in the art, a specific example being pchloro-m-xylenol.

The vinylidene chloride copolymer component of the matte compositions of this invention can be any of the vinylidene chloride copolymers set forth hereinabove (described as suitable for use as subbing layers). Thus, the vinylidene chloride copolymer component of the present matte compositions can contain from about 35 to about 96% of vinylidene chloride, from about 3.5 to about 64.5% of an ethylenicaliy unsaturated ester, from about 0.5 to about 25% of acrylic acid, methacrylic acid, itaconic acid or the half methyl ester thereof. Particularly suitable resins are comprised of, by weight, from about 2% to 10% acrylic or itaconic acid, from about to 60% vinylidene chloride and from about 5% to about 30% of an acrylic compound such as acrylonitrile, ethyl acrylate, methyl acrylate, ethyl methacrylate, methyl methacrylate and the like. Still further preferred are those containing from about 2% to about 8% of acrylic or itaconic acid, from about 83% to about 77% vinylidene chloride, and about 15% of acrylonitrile. Specific examples of such copolymers are (a) a copolymer comprised of, by weight, 15% acrylonitrile, 83% vinylidene chloride, and 2% acrylic acid, and. (b) a copolymer comprised of, by weight, 12% methyl methacrylate, 83% vinylidene chloride, and 5% itaconic acid.

While the preferred abrasive component of the matte compositions of the present invention is silica, other abrasive-type materials having the same average particle size of 2.5 to 10 microns and that will abrade off portions of a marking instrument can be used. Examples of such materials include glass, quartz, diatomaoeous earth, and calcium carbonate. Mixtures of two or more abrasivetype materials can be used if desired. The preferred average particle size of this abrasive component is 5 microns.

The dispersing or wetting agent component of some of the preferred compositions of this invention can be selected from any of a large number of dispersing agents. It is preferred to use anionic or non-ionic type dispersing agents such for example as sodium B,B[-(p-tert-octyl phenoxy)ethoxy] ethane sulfonate (available commercially under the proprietary designation Triton 700), polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate. The above polyoxyethylene compounds are available commercially under the proprietary designation Tween. Saponin can also be used as a dispersing component.

The thickening component of the present matte compositions is an important and critical part of the composition as it assists in providing a coatable composition that is substantially stable and that possesses the desired viscosity. A suitable thickening agent is a colloidally water-soluble polymer of acrylic acid crosslinked with a polyhydroxy compound having at least 3 and preferably not more than about 8 hydroxyl groups, wherein the hydrogen atoms of at least three hydroxyl groups are replaced with unsaturated aliphatic radicals having at least 2 carbon atoms. Preferred radicals are those containing 2 to 4 carbon atoms, e.g., vinyl allyl, crotyl, or other ethylenically unsaturated group. These unsaturated radicals may themselves contain other substituents, such as the methyl group. For example, compounds containing the methallyl radicals are useful.

The crosslinker will comprise about 0.75% to 2.0%, and preferably about 0.75% to 1.5%, by weight, of the polymer of acrylic acid. Best results are obtained with about 1.0% by weight of these polyhydroxy crosslinking materials.

The polydroxy compounds useful as crosslinking materials preferably contain 3 or more hydroxyl groups and can include the saccharides, for example, monosaccharides, such as glucose, fructose, mannose or galactose, and disaccharides, such as sucrose, maltose or lactose. Other useful polyhydroxy compounds include the polyhydroxy alcohols, such as glycerol, erythritol, dulcitol, mannitol, sorbitol and pentaerythritol. The unsaturated crosslinkers described above are all ethers, but also as crosslinking materials there can be used unsaturated esters of the polyhydroxy compounds, such as the triacrylic acid ester of glycerol or acrylic acid esters of sucrose having from 3 to 8 acid residues. Unsaturated ether esters can be used also, but as in the case of unsaturated esters are not preferred because of their tendency to hydrolyze in aqueous solutions. These crosslinking materials are well known in the art.

The preferred crosslinking compounds are polyallyl sucrose or polyallyl pentaerythritol. The polyallyl sucrose and polyallyl pentaerythritol contemplated for use as the crosslinking agent shall desirably contain an average of at least 3 allyl groups for each molecule of sucrose or pentaerythritol. The allyl groups are substituted on the sucrose and pentaerythritol by means of ether linkages; in the case of sucrose a theoretical maximum of 8 allyl groups is possible. For best results the polyallyl sucrose shall contain an average of 5 to '6 allyl ether groups per molecule of sucrose and the polyallyl pentaerythritol shall preferably contain 4 allyl ether groups for each molecule of pentaerythritol (tetraallyl pentaerythritol), which is the maximum theoretically possible for pentaerythritol.

The formation of the crosslinked polymers of acrylic acid is accomplished by polymerizing acrylic acid, or a similar monomer resin-forming material, with one of the aforementioned crosslinking agents in an inert solvent, preferably in the presence of a polymerization catalyst, under autogenous pressure and in an inert atmosphere to inhibit oxidation. The reaction is carried out in the presence of an inert diluent which will not copolymerize with the reactants and which will not cause swelling of the polymerized product. Such diluents shall preferably act as a solvent for the monomeric reactants but not the polymeric reaction product. These diluents include water, a liquid aromatic or aliphatic hydrocarbon such as benzene, toluene, n-hexane or pentane; or an alcohol, such as ethanol, propanol, isopropanol and the like. The liquid hydrocarbons, such as benzene and toluene, are preferred. Preferably the diluent should be employed in a quantity sufllcient to dissolve the reactants, but dissolution is not essential as the polymerization can be con ducted in an aqueous emulsion medium in accordance with standard polymerization practices, although this is not preferred. The polymerization catalyst can be one of the well-known class of free radical catalysts, such as the organic and inorganic peroxides. Specific examples of these include benzoyl peroxide, caproyl peroxide, and sodium or hydrogen peroxide. The catalyst is normally employed in a concentration of about 0.1% to about 1.0%, although it may be as high as 2%, of the weight of the acrylic acid employed.

The polymerization of the acrylic acid and crosslinking agent is preferably carried out with simple agitation in a sealed vessel provided with simple wall-cooling at autogenous pressures. The reaction is an exothermic one and during the polymerization the temperature is desirably maintained between 20 and 70 C., preferably about 50 C. The reaction temperature is not critical, but if held much below 50 C. the rate of polymerization may be quite slow, whereas if the temperature is permitted to go much above 50 C., the exothermic reaction may proceed too rapidly. The polymerization is permitted to proceed as far toward completion as possible, the time re quired varying greatly with the reactants and other factors. If the polymerization is carried out in the presence of an inert diluent as described above, the progress of the reaction can be followed by periodically sampling the liquid phase and analyzing it for the presence of free monomer. In such case, the reaction is determined to be complete when the percentage of monomer reaches a minimum concentration. In practice substantially all of the monomeric material is converted to the polymeric form.

When the polymerization has been completed, the reaction diluent or solvent and the unused catalyst are removed by distillation or filtration. The distillation can be conducted under vacuum. The resulting crosslinked polymer of acrylic acid is a white powder which is somewhat hygroscopic. The polymer is of a rather high molecular weight. While the molecules of the polymer will possess graded molecular weights, the minimum molecular weight of the molecules is desirably in excess of 200,000, and preferably in excess of 300,000.

One particularly suitable colloidally water-soluble polymer of acrylic acid for use in the invention is that available commercially under the proprietary designation Carbopol 934. This product is a colloidally water-soluble polymer of acrylic acid crosslinked with approximately 1% of polyallyl sucrose. This crosslinked polymer is produced by polymerizing acrylic acid monomer with about 1% of its weight of polyallyl sucrose having an average of about 5.8 allyl groups attached through ether linkages to each molecule of sucrose. The polymerization of the acrylic acid monomer is conducted in the presence of toluene diluent and 1% of benzoyl peroxide catalyst in a sealed reaction vessel in accordance with the process described above. After the polymerization has been completed, the toluene is removed by filtration, and the crosslinked polymer which is a white powder having a maximum particle size of 10 mesh and a bulk density of about 12 pounds per cubic foot, is then obtained. The exact molecular weight is unknown, but analysis shows that the product has an equivalent weight (molecular weight for each repeating unit) of about 77. The minimum molecular weight, as roughly determined from viscosity measurements, is about 200,000.

Another suitable thickening agent that can be employed in this invention is poly(rnethyl vinyl e'ther-maleic anhydride) which is the interpolymer of methyl vinyl ether and maleic anhydride. This polymer can be represented by the structural formula wherein n is to 500. A polymer of this type is available commercially under the proprietary designation Gantrez AN In the absence of a thickening agent the solid particles, such as the silica, will settle out of the coating composition in a relatively short period of time. It will be apparent that such a condition is highly undesirable since long runs cannot be satisfactorily carried out. The presence of the thickening agent in the composition will permit coating operations to be carried out satisfactorily for a period of time of about 2 to 3 days, while its absence will permit only about /2 hour of satisfactory coating operation.

In preparing the matte coating composition for use in this invention there is first prepared a substantially stable and uniform aqueous dispersion of thickening component (C), silica component (B), titanium dioxide pigment component and the blue or violet pigment. The pH of this dispersion is desirably adjusted to about 5.5 by the addition thereto of ammonia hydroxide (28% aqueous solution). Suitable dispersions can be prepared by ball milling the components and water for from about 2 hours to about 24 hours. A Kady mill, which is an interia-type mill, can be used to prepare satisfactory dispersions. The amount of water employed is sutficient to provide a pourable paste having a solids content of from about to by weight and a viscosity of from about 10,000 to 50,000 centipoises at 25 C.

A resin latex is prepared which is comprised of vinylidene chloride copolymer (A), dispersing agent and water. The pH of the resin latex is adjusted to about 5.5 by adding ammonia hydroxide thereto. The amount of Water employed is sufiicient to provide a resin latex having a solids content of from about 25% to 35% by weight.

The resin latex is then admixed with the pourable paste above described and the resulting mixture thoroughly admixed to provide an aqueous matte coating composition that is stable and substantially homogeneous.

The following examples are illustrative of this invention. All parts are by "weight unless otherwise indicated.

Example I About 51.3 parts of water, 0.74 part of the water soluble polymer of acrylic acid crosslinked with 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each molecule of sucrose (Carbopol 934), 40 parts of silica having an average particle size of about 5 microns, 6.8 parts of titanium dioxide pigment, 0.011 part of blue pigment (Monarch Blue Toner NCX2371, new color index 74160), 0.004 part of violet pigment (Monastral Violet R RT 7330, color index pigment violet index 19), and 0.62 part of a 4% solution of p-chloro-m-xylenol dissolved in methanol, are ball-milled in a ball mill for about 20 hours to provide a pourable paste. The pH of the paste is adjusted to about 5.5 by adding thereto ammonium hydroxide (28%).

Example II A substantially stable resin latex is prepared by thoroughly admixing about 30 parts of a resin consisting of, by weight, 15% acrylonitrile, 83% vinylidene chloride, and 2% acrylic acid, about 70 parts of water, and about 0.44 part of sodium fi,fi[-(p-tert-octyl phenoxy)] ethane sulfonate (Triton 770). The pH of this latex is adjusted to about 6.4 by adding thereto ammonium hydroxide (28%).

Example III A stable resin latex is prepared by thoroughly admixing about 29 parts of a resin consisting of, by weight, 15% acrylonitrile, 81% vinylidene chloride, and 4% acrylic acid, about 71 parts of water, and about 0.4 part of polyoxyethylene sorbitan monolaurate. The pH of this latex is adjusted to about 6.3 by adding thereto ammonium hydroxide (28% Example IV A pourable paste similar to that of Example I is prepared with the exception that in place of the crosslinked polymer of acrylic acid there is employed an interpolymer of methyl vinyl ether and maleic anhydride having a molecular weight of about 40,000.

Example V A coating composition for application to a subbed surface of polyethylene terephthalate sheeting is prepared by thoroughly admixing about 27 parts of the paste of Example I and about 73 parts of the latex of Example 11.

Example VI A coating composition for application to a subbed surface of polyethylene terephthalate sheeting is prepared by thoroughly admixing about 30 parts of the paste of Example IV with about 70 parts of the resin latex of Example III.

Example VII The coating composition of Example V is applied to the subbed surface of a biaxially oriented polyethylene terephthalate sheet of a thickness of about 5 mils which is subbed on one surface with a sub layer comprised of a resin consisting of, by weight, 15% methacrylate, 83% vinylidene chloride, and 2% itaconic acid in an amount sufficient to provide thereon, 'after drying, a matte surface layer of a thickness of about 0.4 mil. The applied coating composition is dried by conduction heat transfer by impinging air on the uncoated surface of the polyethylene terephthalate sheet material, the air being maintained at a temperature of about 200 F. The resulting article is shown in FIG. 1 of the drawing and is comprised of a polyethylene terephthalate base 10, a sub layer 312, and a matte surface or layer 14. The matte surface layer 14 is firmly bonded, by means of the anchoring or substratum layer 12, to the surface of the polyethylene terephthalate sheet or support 10. The matte surface coating is highly uniform throughout. Substantially no crazing of the matte surface layer is observed. The matte surface layer has good inking and penciling properties, and also good erasure properties.

Example VIII The coating of Example V1 is applied to the subbed surface of a biaxially oriented sheet of polyethylene terephthalate similar to that used in Example VII and in the manner described in Example VII. The matte surface or layer has substantially the same good properties as that of Example VII.

To prepare photographic film products for use in the photographic reproduction art using the matte-surfaced polyester sheeting of this invention the matte surface is overcoated with a substantially unhardened light-sensitive silver halide emulsion layer.

Referring to FIG. 2 of the drawing, there is shown this aspect of the invention. FIG. 2 of the drawing illustrates a photographic film element for use in the photographic reproduction art which is comprised of a polyester film support, in this case polyethylene terephthalate support, 20, a sub layer 22, comprised of a resin consisting of, by weight, 15 percent methacrylate, 83 percent vinylidene chloride, and 2 percent itaconic acid, the matte surface layer 42 of this invention, a gelatin sub layer 26, and an unhardened light-sensitive layer 28. V

Unhardened light-sensitive emulsion layers are wellknown in the art as are the methods for rendering insoluble the exposed portions thereof without affecting the water solubility of the unexposed portions whereby the unexposed portions can be subsequently removed by washing in warm water. Other water soluble materials such as glue and polyvinyl alcohol can be used instead of gelatin in these layers.

A particularly suitable photographic emulsion layer for this purpose is a light-sensitive silver salt emulsion layer containing developing agents such as 3,4-dihydroxy diphenyl; 2,3-dihydroxy diphenyl, and 5,6,7,8-tetrahydronapthohydroquinone. Fine-grain gelatino-silver bromide emulsions are preferred but silver chloride or other silver halide emulsions can be used in gelatin or other vehicles, such as polyvinyl alcohol; which can be differentially tanned with tanning developing agents.

The emulsion layer is exposed in the usual manner under a negative and is developed by immersion in an aqueous soltuion of an alkali such as sodium or potassium carbonate, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or an amine. The addition to the alkaline solution, of other materials, is also helpful in obtaining a satisfactory relief image. For example, the addition of sodium hydroxide to a sodium carbonate solution improves the sensitometric characteristics of the material as well as the H relief properties. The addition of reducing agents such as ascorbic acid, hydrazine hydrochloride, sodium sulfite, in small quantities, sodium bicarbonate and urea, are also advantageous.

After development of the exposed material in the alkaline solution the element is washed with warm water to remove the unexposed and undeveloped colloid and silver halide and then dried, leaving exposed a substantial area of the matte layer.

Emulsions of this type and their method of preparation 9 are disclosed and described in Patent 2,592,368 of Apr. 8, 1952, reference to which is hereby made.

The following example is illustrative of this aspect of the invention.

Example 1X Solutions are made of (i) 25 grams of gelatin in 1 liter of water at 40 C., (ii) 100 grams of silver nitrate in 500 cc. water at C., and (iii) 35 grams of sodium chloride in 500 cc. of water. Solutions (ii) and (iii) are simultaneously run into solution (i) at a uniform rate over a period of about 10 minutes with constant stirring. Thereafter 150 grams of gelatin in 1500 cc. of water at 40 C. are added. The resulting emulsion is then adjusted to a pH of about 5.0. About grams of 2,5-dihydroxy diphenyl dissolved in 250 cc. of methanol is slowly added to the above emulsion with stirring. This emulsion is coated onto the matte surface of the member prepared in Example VII which has been first overcoated with a layer of gelatin and dried. The gelatin layer is applied from an aqueous coating composition consisting of, by weight, 0.66 part of photographic gelatin, 0.03 part of p-chloro-m-xylenol, 0.59 part of methanol, 0.01 part of cetyl betaine, 0.18 part of 'a colloidal silica dispersion, and 98.53 parts of water in an amount sulficient to provide about 0.1 gram of gelatin per square foot of surface. The resulting product is exposed to a suitable negative and developed in a 4% sodium carbonate solution. The developed element is washed with water having a temperature of about 95 F. to remove the unexposed, undeveloped and untanned emulsion. A positive relief image in gelatin is thus obtained with no gelatin remaining on the unexposed areas thereby exposing a portion of the matte surface for pencil and ink drawings and the like.

Also, and in accordance with this invention, it has been determined that the gelatin sub layer as shown in FIG. 2 of the drawing, which is used for the purposes of adequately bonding the applied light-sensitive emulsion layer to the matte surface layer, can be eliminated by employing as the resinous component of the matte surface coating composition a resin comprised of a greater amount of acrylic acid. Thus, if the resin component of the matte coating composition consists of, for example, 15 percent of acrylonitrile, from 77 percent to 81 percent of vinylidene chloride, and from 4 percent to 8 percent of acrylic acid, there is thus provided a matte surface layer to which a light-sensitive silver halide emulsion layer can be applied without the necessity of first applying thereto a gelatin layer.

This aspect of the invention is shown in FIG. 3 of the drawing wherein there is shown a film product comprised of support 30, sub layer 32, matte layer 34 which is comprised of the vinylidene chloride copolymer containing about 4% to 8% of acrylic acid, and an unhardened lightsensitive layer 36.

The matte surface or layer of this invention can be applied so as to provide any desired thickness. Thicknesses of from about 0.2 to 0.6 mil have proven satisfactory in carrying out this invention.

It is to be understood that the above description, drawing, and examples are illustrative of this invention and not in limitation thereof.

What is claimed is:

1. An aqueous composition of matter for use in pro viding a matte surface on polyester sheeting, the solids comprising, by weight,

(A) from about 5 to 30 parts of a copolymer comprised of from about to about 96%, by weight, of vinylidene chloride, from about 3.5 to about 64.5% of an ethylenically unsaturated ester, and from about 0.5 to about 25% of an acidic material selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and the half lower alkyl ester of itaconic acid;

(B) from about 1 part to 25 parts of a finely divided 10 abrasive material having an average particle diameter of from about 2.5 to about 10 microns, and

(C) from about 0.1 to 0.5 part of a thickening agent selected from the group consisting of a colloidally Water-soluble polymer of acrylic acid crosslinked with from about 0.75% to 2.0% of an unsaturated ether of a polyhydroxy compound having at least 3 ethylenically unsaturated double bonds available for crosslinking purposes and an interpolymer of methyl vinyl ether and maleic anhydride.

2. An aqueous composition of matter for use in providing a matte surface on polyester sheeting, the solids comprising, by weight,

(A) from about 5 to 30 parts of a copolymer comprised of, by weight, from about 2% to 10% of acrylic acid or itaconic acid, from about to about 60% of vinylidene chloride, and from about 5% to about 30% of an acrylic compound selected from the group consisting of acrylonitrile, ethyl acrylate, methyl acrylate, methyl methacrylate, and ethyl methacrylate;

(B) from about 1 part to 25 parts of finely divided silica having an average particle size of from about 2.5 to 10 microns; and

(C) from about 0.1 to 0.5 part of a water-soluble polymer of acrylic acid crosslinked with 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each molecule of sucrose.

3. An aqueous composition as in claim 2, wherein said composition additionally contains from about 0.15 part to about 6 parts of a whitening pigment and from about 0.1 to about 1 part of a dispersing agent.

4. An aqueous composition as in claim 3, wherein said whitening pigment is titanium dioxide pigment.

5. A composition of matter for use in providing a matte surfaceon polyester sheeting comprising, by weight,

(A) about 21.9 parts of a copolymer comprised of, by weight, from about 2% to 8% of acrylic acid, from about 83% to 77% of vinylidene chloride, and about 15% of acrylonitrile;

(B) about 10.8 parts of silica having an average particle size of about 5 microns;

(C) about 1.84 parts of titanium dioxide pigment;

(D) about 0.44 part of sodium 13,fi[-(p-tert-octyl phenoxy) ethoxy] ethane sulfonate;

(E) about 0.21 part of a water-soluble polymer of acrylic acid crosslinked with 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each molecule of sucrose;

(F) about 0.011 part of a blue pigment;

(G) about 0.004 part of a violet pigment;

(H) about 0.14 part of 28% ammonium hydroxide;

and I (I) about 64.5 parts of water.

6. An article of manufacture comprised of (1) a polyester sheet,

(2) a sub layer disposed on one surface of the polyester sheet, and

(3) a matte layer on the sub layer comprised of, by

weight,

(A) from about 5 to 30 parts of a copolymer comprised of from about 35% to about 96%, by weight, of vinylidene chloride, from about 3.5 to about 64.5% of an ethylenically unsaturated ester, and from about 0.5 to about 25% of an acidic material selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and the half methyl ester of itaconic acid;

(B) from about 1 part to 25 parts of a finely divided abrasive material having an average particle diameter of from about 2.5 to about 10 microns, and

(C) from about 0.1 to 0.5 part of a thickening agent selected from the group consisting of a colloidally water-soluble polymer of acrylic acid crosslinked with from about 0.75% to 2.0% of an unsaturated ether of a polyhydroxy compound having at least 3 ethylenically unsaturated double bonds available for crosslinking purposes and an interpolymer of methyl vinyl ether and maleic anhydride.

7. An article of manufacture comprised of (1) a polyester sheet,

(2) a sub layer disposed on one surface of the poly- 12 sisting of acrylic acid, methacrylic acid, itaconic acid, and the half methyl ester of itaconic acid;

(B) from about 1 part to 25 parts of a finely divided abrasive material having an average particle diameter of from about 2.5 to about 10 microns;

(C) from about 0.1 to 0.5 part of a thickening agent selected from the group consisting of a colloidally water-soluble polymer of acrylic acid crosslinked with from about 0.75% to 2.0% of ester sheet, and 10 an unsaturated ether of a polyhydroxy corn- (3) a matte layer on the sub layer comprised of, by pound having at least 3 ethylenically unsaturated weight, double bonds available for crosslinking purposes (A) from about 5 to 30 parts of a copolymer comof an interpolymer of methyl vinyl ether and prised of, by Weight, from about 2% to maleic anhydride, and of acrylic acid or itaconic acid from about 90% (4) an unhardened light-sensitive layer disposed over to 60% of vinylidene chloride, and from about the matte layer (3). 5% to about 30% of an acrylic compound se- 13. A photographic film product as in claim 12, wherelected from the group consisting of acrylonitrile in said matte layer is comprised of ethyl acrylate, methyl acrylate, methyl meth- (A) from about 5 to 30 parts of a copolymer comacrylate, and ethyl methacrylate; prised of, by weight, from about 2% to 10% of acryl- (B) from about 1 part to parts of finely divided ic acid or itaconic acid, from about 90% to 60% of silica having an average particle size of from vinylidene chloride, and from about 5% to about about 2.5 to 10 microns; and of an acrylic compound selected from the group (C) from about 0.1 to 0.5 part of a water-soluble 25 consisting of acrylonitrile ethyl acrylate, methyl acrypoly-mer of acrylic acid crosslinked With 1% late, methyl methacrylate, and ethyl methacrylate; of a polyallyl ester of sucrose having an aver- (B) from about 1 part to 25 parts of finely divided age of about 5.8 allyl groups for each molecule silica having an average particle size of from about of sucrose. 2.5 to 10 microns; and 8. An article of manufacture comprised of 30 (C) from about 0.1 to 0.5 part of a water-soluble (1) a polyester sheet, polymer of acrylic acid crosslinked with 1% of a (2) a sub layer disposed on one surface of the polypolyallyl ether of sucrose having an average of about ester sheet, and 5.8 allyl groups for each molecule of sucrose. (3) a matte layer on the sub layer comprised of, by 14. A photographic film product as in claim 13, Where- Weight, in said matte layer and said sub layer are on both surfaces (A) about 21.9 parts of a copolymer comprised of, of said sheet.

by weight, from about 2% to 8% of acrylic acid, 15. A photographic film product as in claim 13, where from about 83% to 77% of vinylidene chloride, in said light-sensitive layer is a silver halide emulsion and about 15% of acrylonitrile; layer. (B) about 10.8 parts of silica having an average 16. A photographic film product as in claim 15, whereparticle size of about 5 microns; in said matte layer is comprised of (C) about 1.84 parts of titanium dioxide pigment; (A) about 21.9 parts of a copolymer comprised of, by D) about 0.21 part of a water-soluble polymer weight, from about 2% to 8% of acrylic acid, from of acrylic acid crosslinked with 1% of a polyabout 83% to 77% of vinylidene chloride, and about allyl ether of sucrose having an average of about 15% of acrylonitrile; 5.8 allyl groups for each molecule of sucrose; (B) about 10.8 parts of silica having an average par- (E) about 0.011 part of a blue pigment; ticle size of about 5 microns; (F) about 0.004 part of a violet pigment. (C) about 1.84 parts of titanium dioxide pigment; 9. The article of claim 7 wherein the polyester sheet (D) about 0.21 part of a water-soluble polymer of (1) is a polyethylene terephthalate sheet. acrylic acid crosslinked With 1% of a polyallyl ether 10. The articles of claim 9, wherein said matte layer of sucrose having an average of about 5.8 allyl groups and said sub layer are on both surfaces of said polyethylfor each molecule of sucrose;

ene terephthalate sheet. (E) about 0.011 part of a blue pigment;

11. The article of claim 8 wherein the polyester sheet (F) about 0.004 part of a violet pigment.

(1) is a polyethylene terephthalate sheet. 17. A photographic film product as in claim 15, where- 12. A photographic film product comprised of in said matte layer and said sub layer are on both surfaces (1) a sheet of polyethylene terephthalate of said sheet.

(2) a sub layer on one surface of sheet (1) References Cited (3)Nezi1glr3atte layer on the sub layer comprised of, by UNITED STATES PATENTS (A) from about 5 to 0 parts of a copolymer 2,780,562 2/1957 Reinartz et a1. 26029.6 X prised of from about 35% to about 96%, by 2,798,053 7/1957 Brown 26O 17'4 X weight, of vinylidene chloride, from about 3.5 2,914,498 11/1959 Quarks at 26O29-6 to about 64.5% of an ethylenically unsaturated ester, and from about 0.5 to about 25% of an NORMAN TORCHIN Prmmry Exammer' acidic material selected from the group con- R. H. SMITH, Examiner. 

1. AN AQUEOUS COMPOSITION OF MATTER FOR USE IN PROVIDING A MATTE SURFACE ON POLYVESTER SHEETING, THE SOLIDS COMPRISING, BY WEIGHT, (A) FROM ABOUT 5 TO 30 PARTS OF A COPOLYMER COMPRISED OF FROM ABOUT 35% TO ABOUT 96%, BY WEIGHT, OF VINYLIDENE CHLORIDE, FROM ABOUT 3.5 TO ABOUT 64.5% OF AN ETHYLENICALLY UNSATURATED ESTER, AND FROM ABOUT 0.5 TO ABOUT 25% OF AN ACIDIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF ACRYLIC ACID, METHACRYLIC ACID, ITACONIC ACID, AND THE HALF LOWER ALKYL ESTER OF ITACONIC ACID; (B) FROM ABOUT 1 PART TO 25 PARTS OF A FINELY DIVIDED ABRASIVE MATERIAL HAVING AN AVERAGE PARTICLE DIAMETER OF FROM ABOUT 2.5 TO ABOUT 10 MICRONS, AND (C) FROM ABOUT 0.1 TO 0.5 PART OF A THICKENING AGENT SELECTED FROM THE GROUP CONSISTING OF A COLLOIDALLY WATER-SOLUBLE POLYMER OF ACRYLIC ACID CROSSLINKED WITH FROM ABOUT 0.75% TO 2.0% OF AN UNSATURATED ETHER OF A POLYHYDROXY COMPOUND HAVING AT LEAST 3 ETHYLENICALLY UNSATURATED DOUBLE BONDS AVAILABLE FOR CROSSLINKING PURPOSES AND AN INTERPOLYMER OF METHYL VINYL ETHER AND MALEIC ANHYDRIDE.
 6. AN ARTICLE OF MANUFACTURE COMPRISED OF (1) A POLYESTER SHEET, (2) A SUB LAYER DISPOSED ON ONE SURFACE OF THE POLYESTER SHEET, AND (3) A MATTE LAYER ON THE SUB LAYER COMPRISED OF, BY WEIGHT, (A) FROM ABOUT 5 TO 30 PARTS OF A COPOLYMER COMPRISED OF FROM ABOUT 35% TO ABOUT 96%, BY WEIGHT, OF VINYLIDENE CHLORIDE, FROM ABOUT 3.5 TO ABOUT 64.5% OF AN ETHYLENICALLY UNSATURATED ESTER, AND FROM ABOUT 0.5 TO ABOUT 25% OF AN ACIDIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF ACRYLIC ACID, METHYACRYLIC ACID, ITACONIC ACID, AND THE HALF METHYL ESTER OF ITACONIC ACID; (B) FROM ABOUT 1 PART TO 25 PARTS OF A FINELY DIVIDED ABRASIVE MATERIAL HAVING AN AVERAGE PARTICLE DIAMETER OF FROM ABOUT 2.5 TO ABOUT 10 MICRONS, AND (C) FROM ABOUT 0.1 TO 0.5 PART OF A THICKENING AGENT SELECTED FROM THE GROUP CONSISTING OF A COLLOIDALLY WATER-SOLUBLE POLYMER OF ACRYLIC ACID CROSSLINKED WITH FROM ABOUT 0.75% TO 2.0% OF AN UNSATURATED ETHER OF A POLYHYDROXY COMPOUND HAVING AT LEAST 3 ETHYLENICALLY UNSATURATED DOUBLE BONDS AVAILABLE FOR CROSSLINKING PURPOSES AND AN INTERPOLYMER OF METHYL VINYL ETHER AND MALEIC ANHYDRIDE.
 12. A PHOTOGRAPHIC FILM PRODUCT COMPRISED OF (1) A SHEET OF POLYETHYLENE TEREPHTHALATE (2) A SUB LAYER ON ONE SURFACE OF SHEET (1) (3) A MATTE LAYER ON THE SUB LAYER COMPRISED OF, BY WEIGHT, (A) FROM ABOUT 5 TO 30 PARTS OF A COPOLYMER COMPRISED OF FROM ABOUT 35% TO ABOUT 96%, BY WEIGHT, OF VINYLDENE CHLORIDE, FROM ABOUT 3.5 TO ABOUT 64.5% OF AN ETHYLENICALLY UNSATURATED ESTER, AND FROM ABOUT 0.5 TO ABOUT 25% OF AN ACIDIC MATERIAL SELECTED FROMTHE GROUP CONSISTING OF ACRYLIC ACID, METHACRYLIC ACIDD, ITACONIC ACID, AND THE HALF METHYL ESTER OF ITACONIC ACID; (B) FROM ABOUT 1 PART TO 25 PARTS OF A FINELY DIVIDED ABRASIVE MATERIAL HAVING AN AVERAGE PARTICLE DIAMETER OF FROM ABOUT 2.5 TO ABOUT 10 MICRONS; (C) FROM ABOUT 0.1 TO 0.5 PART OF A THICKENING AGENT SELECTED FROM THE GROUP CONSISTING OF A COLLOIDALLY WATER-SOLUBLE POLYMER OF ACRYLIC ACID CROSSLINKED WITH FROM ABOUT 0.75% TO 2.0% OF AN UNSATURATED ETHER OF A POLYHYDROXY COMPOUND HAVING AT LEAST 3 ETHYLENICALLY UNSATURATED DOUBLE BONDS AVAILABLE FOR CROSSLINKING PURPOSES OF AN INTERPOLYMER OF METHYL VINYL ETHER AND MALEIC ANHYDRIDE, AND (4) AN UNHARDENED LIGHT-SENSITIVE LAYER DISPOSED OVER THE MATTE LAYER (3). 